マンガンで触媒化された後期アリファティックC-Hアジデーション
Xiongyi Huang1, Tova M Bergsten1, John T Groves1
1Department of Chemistry, Princeton University, Princeton, New Jersey 08544 United States.
Journal of the American Chemical Society
|April 15, 2015
まとめ
この研究では,水性ナトリウムアジドを使用してC-H結合をアジドに変換するためのマンガン触媒反応を導入しています. この効率的な方法により,生物活性分子の後期機能化が可能になり,エナチオセレクティブC-Hアジデーションが実証されています.
科学分野:
- 有機化学 オーガニック・ケミストリー
- カタリシス カタリシス カタリシス
- 薬用化学 薬用化学について
背景:
- アリファティックC-H結合は有機分子に至る所に存在します.
- オーガニック・アジドは,合成における多用途の中間物質である.
- C-H機能化の効率的な方法は,非常に求められています.
研究 の 目的:
- アリファティックC-Hアジデーションのマンガン触媒法を開発する.
- 生物活性化合物の後期機能化におけるこの反応の有用性を実証する.
- エナチオセレクティブC-Hアジデーションを達成するために.
主な方法:
- 水性ナトリウムアジドを用いたマンガン触媒反応.
- エアロビック条件下で実行される反応.
- 二次,三次,およびベンジルC-H結合への適用.
主要な成果:
- C-Hボンドをアジドに効率的に変換し,利回りは最大74%です.
- プレガバリン,メマンチン,アルテミシニンなどの薬物の後期アジデーションの成功.
- Mn触媒によるエナチオセレクティブアジデーションで70%のエナチオメア過剰 (ee) を達成した.
結論:
- 開発されたMn-azidation方法は,操作的にはシンプルで効率的です.
- この方法は,薬剤発見と化学生物学にとって大きな可能性を秘めています.
- エナチオセレクティブC-Hアジデーションは,この変換の合成的有用性を拡大します.
さらに関連する動画
関連する概念動画
01:21Radical Oxidation of Allylic and Benzylic Alcohols
3.2K
Activated manganese(IV) oxide can selectively oxidize allylic and benzylic alcohols via a radical intermediate mechanism. Primary allylic alcohols are oxidized to aldehydes, while secondary allylic alcohols yield ketones. The redox reaction of potassium permanganate with an Mn(II) salt such as manganese sulfate (under either alkaline or acidic conditions), followed by thorough drying, yields the oxidizing agent: activated MnO2. While MnO2 is insoluble in the solvents used for the reaction, the...
3.2K
01:22Preparation of 1° Amines: Azide Synthesis
4.9K
Direct alkylation of ammonia produces polyalkylated amines, along with a quaternary ammonium salt. To exclusively prepare primary amines, the azide synthesis method can be used.
Azide ions act as good nucleophiles and react with unhindered alkyl halides to form alkyl azides. Alkyl azides do not participate in further nucleophilic substitution reactions, thereby eliminating the chances of polyalkylated products. Alkyl azides are reduced by hydride-based reducing agents, like lithium aluminum...
Azide ions act as good nucleophiles and react with unhindered alkyl halides to form alkyl azides. Alkyl azides do not participate in further nucleophilic substitution reactions, thereby eliminating the chances of polyalkylated products. Alkyl azides are reduced by hydride-based reducing agents, like lithium aluminum...
4.9K
02:24Reduction of Alkynes to cis-Alkenes: Catalytic Hydrogenation
9.6K
Introduction
Like alkenes, alkynes can be reduced to alkanes in the presence of transition metal catalysts such as Pt, Pd, or Ni. The reaction involves two sequential syn additions of hydrogen via a cis-alkene intermediate.
Like alkenes, alkynes can be reduced to alkanes in the presence of transition metal catalysts such as Pt, Pd, or Ni. The reaction involves two sequential syn additions of hydrogen via a cis-alkene intermediate.
9.6K
01:21Acid-Catalyzed α-Halogenation of Aldehydes and Ketones
5.3K
By replacing an α-hydrogen with a halogen, acid-catalyzed α-halogenation of aldehydes or ketones yields a monohalogenated product
In the first step of the mechanism, the acid protonates the carbonyl oxygen resulting in a resonance-stabilized cation, which subsequently loses an α-hydrogen to form an enol tautomer. The C=C bond in an enol is highly nucleophilic because of the electron-donating nature of the –OH group. Consequently, the double bond attacks an electrophilic...
In the first step of the mechanism, the acid protonates the carbonyl oxygen resulting in a resonance-stabilized cation, which subsequently loses an α-hydrogen to form an enol tautomer. The C=C bond in an enol is highly nucleophilic because of the electron-donating nature of the –OH group. Consequently, the double bond attacks an electrophilic...
5.3K
02:17Reduction of Alkenes: Asymmetric Catalytic Hydrogenation
4.1K
Catalytic hydrogenation of alkenes is a transition-metal catalyzed reduction of the double bond using molecular hydrogen to give alkanes. The mode of hydrogen addition follows syn stereochemistry.
The metal catalyst used can be either heterogeneous or homogeneous. When hydrogenation of an alkene generates a chiral center, a pair of enantiomeric products is expected to form. However, an enantiomeric excess of one of the products can be facilitated using an enantioselective reaction or an...
The metal catalyst used can be either heterogeneous or homogeneous. When hydrogenation of an alkene generates a chiral center, a pair of enantiomeric products is expected to form. However, an enantiomeric excess of one of the products can be facilitated using an enantioselective reaction or an...
4.1K
02:21Oxidation of Alkenes: Syn Dihydroxylation with Potassium Permanganate
18.6K
Alkenes can be dihydroxylated using potassium permanganate. The method encompasses the reaction of an alkene with a cold, dilute solution of potassium permanganate under basic conditions to form a cis-diol along with a brown precipitate of manganese dioxide.
18.6K